EP1922368B1 - Matieres d'enduction contenant des nanoparticules d'oxyde mixte - Google Patents

Matieres d'enduction contenant des nanoparticules d'oxyde mixte Download PDF

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Publication number
EP1922368B1
EP1922368B1 EP06776872.1A EP06776872A EP1922368B1 EP 1922368 B1 EP1922368 B1 EP 1922368B1 EP 06776872 A EP06776872 A EP 06776872A EP 1922368 B1 EP1922368 B1 EP 1922368B1
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EP
European Patent Office
Prior art keywords
mixed oxide
oxide nanoparticles
nanoparticles
alkyl
der
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Not-in-force
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EP06776872.1A
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German (de)
English (en)
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EP1922368A2 (fr
Inventor
Norbert RÖSCH
Ernst Krendlinger
Anja Heinze
Karl Zeisberger
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Archroma IP GmbH
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Clariant Finance BVI Ltd
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Priority claimed from DE102005039436A external-priority patent/DE102005039436B4/de
Priority claimed from DE102006021705A external-priority patent/DE102006021705B3/de
Application filed by Clariant Finance BVI Ltd filed Critical Clariant Finance BVI Ltd
Priority to PL06776872T priority Critical patent/PL1922368T3/pl
Publication of EP1922368A2 publication Critical patent/EP1922368A2/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C09C1/407—Aluminium oxides or hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/40—Compounds of aluminium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds

Definitions

  • Nanoparticles containing coating compositions are known, wherein the nanoparticles are prepared by sol-gel technique by hydrolytic (co) condensation of tetraethoxysilane (TEOS) with other metal alkoxides in the absence of organic and / or inorganic binders.
  • TEOS tetraethoxysilane
  • sol-gel synthesis can also be carried out in the medium. Radiation-curing formulations are preferably used.
  • all materials produced by sol-gel process are characterized by low solids contents of inorganic and organic substance, by increased amounts of the condensation product (usually alcohols), by the presence of water and by limited storage stability.
  • Nanoscale surface-modified particles (Degussa Aerosil® R 7200), which are formed by condensation of metal oxides with silanes in the absence of a binder and thus in the absence of strong shear forces, as they act in viscous media at stirring speeds of ⁇ 10 m / s. These aerosils therefore have larger particles than the raw materials used, their opacity is significantly higher and their effectiveness is less than the effect of in WO 00/22052 described particles and the varnishes produced therefrom.
  • WO 2004/069400 A1 discloses a method for producing surface-modified nanoscale colloid particles.
  • DE 1068836 A1 describes spinel type compounds as pigments and fillers.
  • the object of the invention is to eliminate the disadvantages of the prior art and to provide storage and property stable coating compositions containing specially prepared nanoscale inorganic particles.
  • the invention relates to coating compositions comprising mixed oxide nanoparticles consisting of 50-99.9% by weight of aluminum oxide and 0.1-50% by weight of oxides of elements of the 1st or 2nd main group of the periodic table.
  • the alumina in these mixed oxides is for the most part in the rhombohedral ⁇ -modification (corundum) and the mixed oxide nanoparticles are modified with a silane or siloxane on the surface.
  • the mixed oxides according to the present invention preferably have a crystallite size of less than 1 ⁇ m, preferably less than 0.2 ⁇ m and particularly preferably between 0.001 and 0.09 ⁇ m. Particles of this size according to the invention will be referred to below as mixed oxide nanoparticles.
  • the mixed oxide nanoparticles according to the invention can be prepared by different processes described below. These process descriptions refer to the production of only pure alumina particles, but it goes without saying that in all these process variants in addition to Al-containing starting compounds and those must be present to form the mixed oxides according to the invention.
  • the chlorides especially the chlorides, but also the oxides, oxide chlorides, carbonates, sulfates or other suitable salts come into question.
  • the amount of such oxide formers is such that the finished nanoparticles contain the aforementioned amounts of oxide MeO.
  • agglomerates of these mixed oxides are used, which are then deagglomerated to the desired particle size.
  • These agglomerates can be prepared by methods described below.
  • Such agglomerates can be prepared, for example, by various chemical syntheses. These are usually precipitation reactions (hydroxide precipitation, hydrolysis of organometallic compounds) with subsequent calcination. Crystallization seeds are often added to reduce the transition temperature to the ⁇ -alumina. The sols thus obtained are dried and thereby converted into a gel. The further calcining then takes place at temperatures between 350 ° C and 650 ° C. For the conversion to ⁇ -Al 2 O 3 must then be annealed at temperatures around 1000 ° C. The procedures are detailed in DE 199 22 492 described.
  • the desired molecules are obtained from chemical reactions of a Precursorgases or by rapid cooling of a supersaturated gas.
  • the formation of the particles occurs either through collision or the constant equilibrium evaporation and condensation of molecular clusters.
  • the newly formed particles grow by further collision with product molecules (condensation) and / or particles (coagulation). If the coagulation rate is greater than that of the new growth or growth, agglomerates of spherical primary particles are formed.
  • Flame reactors represent a production variant based on this principle. Nanoparticles are produced here by the decomposition of Precursor molecules formed in the flame at 1500 ° C - 2500 ° C. As examples, the oxidations of TiCl 4 ; SICl 4 and Si 2 O (CH 3 ) 6 are mentioned in methane / O 2 flames leading to TiO 2 and SiO 2 particles. When using AlCl 3 so far only the corresponding clay could be produced. Flame reactors are now used industrially for the synthesis of submicroparticles such as carbon black, pigment TiO 2 , silica and alumina.
  • Small particles can also be formed from drops with the help of centrifugal force, compressed air, sound, ultrasound and other methods.
  • the drops are then converted into powder by direct pyrolysis or by in situ reactions with other gases.
  • the spray and freeze drying should be mentioned.
  • precursor drops are transported through a high temperature field (flame, oven), resulting in rapid evaporation of the volatile component or initiating the decomposition reaction to the desired product.
  • the desired particles are collected in filters.
  • the production of BaTiO 3 from an aqueous solution of barium acetate and titanium lactate can be mentioned here.
  • the nanoparticles must be released. This is preferably done by grinding or by treatment with ultrasound. According to the invention, this deagglomeration is carried out in the presence of a solvent and a silane or siloxane to modify the surface, which saturates the resulting active and reactive surfaces during the milling process by a chemical reaction or physical attachment and thus prevents reagglomeration.
  • the nano-mixed oxide remains as a small particle. It is also possible to add the silane or siloxane for the modification of the surface after deagglomeration.
  • the starting point here is aluminum chlorohydrate, which has the formula Al 2 (OH) x Cl y , where x is a number from 2.5 to 5.5 and y is a number from 3.5 to 0.5 and the sum of x and y always 6.
  • This aluminum chlorohydrate is mixed with crystallization seeds as an aqueous solution, then dried and then subjected to a thermal treatment (calcination).
  • aqueous solutions Preference is given to starting from about 50% aqueous solutions, as they are commercially available. Such a solution is added with seed crystals that promote the formation of the ⁇ -modification of Al 2 O 3 .
  • nuclei cause a lowering of the temperature for the formation of the ⁇ -modification in the subsequent thermal treatment.
  • germs are preferably in question finely disperse corundum, diaspore or hematite.
  • Particular preference is given to taking very finely divided ⁇ -Al 2 O 3 nuclei having an average particle size of less than 0.1 ⁇ m. In general, 2 to 3 wt .-% of germs based on the resulting alumina from.
  • This starting solution additionally contains oxide formers in order to produce the oxides MeO in the mixed oxide.
  • oxide formers for this come in particular the chlorides of Elements of the I and II. Main group of the Periodic Table, in particular the chlorides of the elements Ca and Mg, but also other soluble or dispersible salts such as oxides, oxychlorides, carbonates or sulfates.
  • the amount of oxide generator is such that the finished nanoparticles contain from 0.01 to 50% by weight of the oxide Me.
  • the oxides of the I. and II. Main group may be present as a separate phase in addition to the alumina or with this real mixed oxides such as spinels, etc. form.
  • mixed oxides in the context of this invention should be understood to include both types.
  • This suspension of aluminum chlorohydrate, germs and oxide formers is then evaporated to dryness and subjected to a thermal treatment (calcination).
  • This calcination is carried out in suitable devices, for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • suitable devices for example in push-through, chamber, tube, rotary kiln or microwave ovens or in a fluidized bed reactor.
  • the temperature for the calcination should not exceed 1400 ° C.
  • the lower temperature limit depends on the desired yield of nanocrystalline mixed oxide, the desired residual chlorine content and the content of germs.
  • the formation of the nanoparticles begins at about 500 ° C, but to keep the chlorine content low and the yield of nanoparticles high, but it is preferably at 700 to 1100 ° C, especially at 1000 to 1100 ° C work.
  • agglomerates accumulate in the form of nearly spherical nanoparticles. These particles consist of Al 2 O 3 and MeO. The content of MeO acts as an inhibitor of crystal growth and keeps the crystallite size small. As a result, the agglomerates, as obtained by the calcination described above, clearly differ from the particles, as in the WO 2004/069 400 be used, where it is coarser, in itself homogeneous particles and not agglomerates of already prefabricated nanoparticles.
  • the agglomerates are preferably comminuted by wet grinding in a solvent, for example in an attritor mill, bead mill or stirred mill.
  • a solvent for example in an attritor mill, bead mill or stirred mill.
  • a suspension of nanoparticles with a d90 value of approximately 50 nm is obtained.
  • Another possibility for deagglomeration is sonication.
  • deagglomeration can be carried out in the presence of silanes or siloxanes, for example by adding the silane or siloxane to the mill during milling.
  • a second possibility consists in first destroying the agglomerates of the nanoparticles and then treating the nanoparticles, preferably in the form of a suspension in a solvent, with the silane or siloxane.
  • Suitable solvents for deagglomeration are both water and conventional solvents, preferably those which are also used in the paint industry, such as, for example, C 1 -C 4 -alcohols, in particular methanol, ethanol or isopropanol, acetone, tetrahydrofuran, butyl acetate.
  • an inorganic or organic acid For example, HCl, HNO 3 , formic acid or acetic acid are added to stabilize the resulting nanoparticles in the aqueous suspension.
  • the amount of acid may be 0.1 to 5 wt .-%, based on the mixed oxide.
  • aqueous suspension of the acid-modified nanoparticles is then preferably the grain fraction having a particle diameter of less than 20 nm separated by centrifugation.
  • the coating agent for example at about 100 ° C, the coating agent, a silane or siloxane, is added.
  • the nanoparticles thus treated precipitate are separated and dried to a powder, for example by freeze-drying.
  • Suitable coating agents here are silanes or siloxanes or mixtures thereof.
  • the coating agents, the silanes or siloxanes are preferably added in molar ratios of mixed oxide nanoparticles to silane of 1: 1 to 10: 1.
  • the amount of solvent during deagglomeration is generally 80 to 90 wt .-%, based on the total amount of mixed oxide nanoparticles and solvent.
  • the deagglomeration by grinding and simultaneous modification with the coating agent is preferably carried out at temperatures of 20 to 150 ° C, more preferably at 20 to 90 ° C.
  • the suspension is subsequently separated from the grinding beads.
  • the suspension can be heated to complete the reaction for up to 30 hours. Finally, the solvent is distilled off and the remaining residue is dried. It may also be advantageous to leave the modified mixed oxide nanoparticles in the solvent and to use the dispersion for other applications.
  • the binder may also be selected to be identical to the silane used for functionalization.
  • the binders preferably have a molecular weight of 100 to 800 g / mol.
  • the content of binder in the entire coating composition is preferably 80 to 99, in particular 90 to 99 wt .-%.
  • the coating compositions according to the invention may also contain other additives, as are customary in paint technology, for example reactive diluents, solvents and co-solvents, waxes, matting agents, lubricants, defoamers, deaerators, leveling agents, thixotropic agents, thickeners, inorganic and organic pigments, fillers, adhesion promoters , Corrosion inhibitors, anti-corrosive pigments, UV stabilizers, HALS compounds, radical scavengers, antistatic agents, wetting agents and dispersants and / or required depending on the type of curing catalysts, co-catalysts, initiators, free-radical initiators, photoinitiators, photosensitizers, etc.
  • additives for example reactive diluents, solvents and co-solvents, waxes, matting agents, lubricants, defoamers, deaerators, leveling agents, thixotropic agents, thickeners,
  • additives include polyethylene glycol and other water retention agents, PE waxes, PTFE waxes, PP waxes, amide waxes, FT paraffins, montan waxes, grafted waxes, natural waxes, macro- and microcrystalline paraffins, polar polyolefin waxes, sorbitan esters, polyamides, polyolefins, PTFE, wetting agents or silicates in question.
  • a 50% aqueous solution of aluminum chlorohydrate was added with magnesium chloride so that after calcination the ratio of alumina to magnesium oxide was 99.5: 0.5%.
  • 2% of nuclei were added to the solution to a suspension of fines. After the solution has been homogenized by stirring, the drying is carried out in a rotary evaporator. The solid aluminum chlorohydrate magnesium chloride mixture was crushed in a mortar to form a coarse powder.
  • the powder was calcined in a rotary kiln at 1050 ° C.
  • the contact time in the hot zone was a maximum of 5 min.
  • a white powder was obtained whose grain distribution corresponded to the feed material.
  • An X-ray structure analysis shows that predominantly ⁇ -alumina is present.
  • the images of the SEM image taken showed crystallites in the range 10 - 80 nm (estimate from SEM image), which are present as agglomerates.
  • the residual chlorine content was only a few ppm.
  • Example 1 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 3 hours, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. To the suspension was added 40 g of trimethoxy-octylsilane and heated at reflux for 2 h. After removal of the solvent, the coated oxide mixture was isolated and dried in an oven for another 20 h at 110 ° C. The product thus obtained is identical to the sample from Example 1.
  • the oxide mixture MgO-doped corundum
  • Example 2 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, 20 g of 3- (trimethoxysilyl) propyl methacrylate (Dynasilan Memo, Degussa) were added and the suspension was deagglomerated in the stirred ball mill for a further 2 h. Subsequently, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. Reflux was continued for an additional 2 hours before the solvent was distilled off.
  • the oxide mixture MgO-doped corundum
  • Example 2 40 g of the oxide mixture (MgO-doped corundum) from Example 1 was suspended in 160 g of methanol and deagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, 20 g
  • Example 2 40 g of the oxide mixture (doped with MgO corundum) from Example 1 was suspended in 160 g of acetone and disagglomerated in a vertical stirred ball mill from. Netzsch (type PE 075). After 2 h, 20 g of glycidyltrimethoxysilane (Dynasilan Glymo, Degussa) were added and the suspension was deagglomerated for a further 2 hours in the recycle ball mill. Subsequently, the suspension was separated from the beads and transferred to a round bottom flask with reflux condenser. Reflux was continued for an additional 2 hours before the solvent was distilled off.
  • glycidyltrimethoxysilane Dynasilan Glymo, Degussa
  • Example 2 40 g of the oxide mixture (MgO doped corundum) from Example 1 was suspended in 160 g of n-butanol and disagglomerated in a vertical stirred ball mill from Netzsch (type PE 075). After 2 h, a mixture of 5 g of aminopropyltrimethoxysilane (Dynasilan Ammo, Degussa) and 15 g of octyltriethoxysilane was added and the suspension was deagglomerated in the stirred ball mill for an additional 2 hours. The suspension remains stable for weeks without evidence of sedimentation of the coated mixed oxide.
  • the oxide mixture MgO doped corundum
  • the coated mixed oxides from the examples were tested in various paint systems for their abrasion resistance, hardness, gloss and scratch resistance. The tests are carried out in a 2-component polyurethane paint system, a 100% UV paint system and a 1-component stoving enamel system.
  • the samples from Examples 1-3 were dispersed in the first component or in a solvent of the coating system.
  • the paints were applied to glass plates with a wet film thickness of 60 ⁇ m and the gloss was determined by means of the micro-gloss from BYK-Gardner at an angle of 60 °. Gloss / 60 ° without additive 144 2% mixed oxide nanoparticles / Ex. 3 133 4% mixed oxide nanoparticles / example 3 129 4% mixed oxide nanoparticles / Ex. 1 or 2 126 6% mixed oxide nanoparticles / example 1 or 2 120 10% mixed oxide nanoparticles / example 1 or 2 110
  • the hardness was determined by determining the pencil hardness according to Wolff-Wilborn. hardness without Additive F 10% mixed oxide nanoparticles / example 1 or 2 F 6% mixed oxide nanoparticles / example 1 or 2 F 4% mixed oxide nanoparticles / Ex. 1 or 2 H 4% mixed oxide nanoparticles / example 3 H 4% mixed oxide nanoparticles / example 3 H soft 6B 5B 4B 3B 2 B B HB F H 2H 3H 4H 5H 6H 7H 8H 9H hard
  • the paints were applied to glass plates with a wet film thickness of 60 ⁇ m and the gloss was determined by means of the micro-gloss from BYK-Gardner at an angle of 60 °. shine without additives 139 2% mixed oxide nanoparticles / Ex. 3 137 2% mixed oxide nanoparticles / example 1 or 2 120
  • the hardness was determined by means of the pencil hardness according to Wolff-Wilborn. hardness soft without additives H ⁇ 2% mixed oxide nanoparticles / Ex. 3 H 2% mixed oxide nanoparticles / example 1 or 2 2H hard
  • the samples from Examples 4 to 6 were dispersed in the paint or in a solvent of the paint system.
  • the paints were applied to glass plates with a wet film thickness of 60 ⁇ m and the gloss was determined by means of the micro-gloss from BYK-Gardner at an angle of 60 °. shine without additives 154 2% mixed oxide nanoparticles / Ex. 4 150 2% mixed oxide nanoparticles / Ex. 5 138 5% mixed oxide nanoparticles / Ex. 4 146 5% mixed oxide nanoparticles / Ex. 5 123 shine without additives 154 2% mixed oxide nanoparticles / Ex. 6 142 4% mixed oxide nanoparticles / Ex. 6 130
  • the paints were applied to tinned tinplate with a 60 ⁇ m wet film thickness and the scratch hardness was determined by the number of strokes.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Wood Science & Technology (AREA)
  • Composite Materials (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Silicon Polymers (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Claims (5)

  1. Compositions de revêtement comprenant des nanoparticules d'oxydes mixtes, comprenant de 50 % à 99,9 % en poids d'oxyde d'aluminium, dans lesquelles l'oxyde d'aluminium est présent de manière prédominant dans la modification rhomboédrique alpha, et de 0,1 % à 50 % en poids d'oxydes d'éléments appartenant au groupe I ou II principal de la Table périodique des éléments, et dans lesquelles les nanoparticules d'oxydes mixtes sont modifiées en surface par un silane ou un siloxane.
  2. Compositions de revêtement selon la revendication 1 caractérisées en ce que lesdites compositions de revêtement comprennent des nanoparticules d'oxydes mixtes qui sont formées par désagglomération d'agglomérats de nanoparticules d'oxydes mixtes par broyage des nanoparticules d'oxydes mixtes dans un solvant.
  3. Compositions de revêtement selon la revendication 1 caractérisées en ce que lesdites compositions de revêtement comprennent des nanoparticules qui sont modifiées en surface par un matériau de revêtement, et dans lesquelles les nanoparticules modifiées en surface sont formées par désagglomération d'agglomérats comprenant des nanoparticules d'oxydes mixtes par broyage dans un solvant et traitement simultané avec le matériau de revêtement de modification de surface.
  4. Compositions de revêtement selon la revendication 1 caractérisées en ce que lesdites compositions de revêtement comprennent des nanoparticules d'oxydes mixtes qui sont modifiées en surface par un matériau de revêtement, et dans lesquelles les nanoparticules d'oxydes mixtes modifiées en surface sont formées par désagglomération d'agglomérats comprenant des nanoparticules d'oxydes mixtes par broyage dans un solvant et traitement simultané avec le matériau de revêtement de modification de surface.
  5. Compositions de revêtement selon l'une quelconque des revendications 1 à 4 caractérisées en ce que ladite composition de revêtement est un vernis.
EP06776872.1A 2005-08-18 2006-08-16 Matieres d'enduction contenant des nanoparticules d'oxyde mixte Not-in-force EP1922368B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL06776872T PL1922368T3 (pl) 2005-08-18 2006-08-16 Masy powłokowe, zawierające nanocząstki tlenków mieszanych, składające się z 50-99,9 % wag. al203 i 0,1-50 % wag. tlenków pierwiastków i-szej lub ii-giej grupy głównej układu okresowego

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102005039436A DE102005039436B4 (de) 2005-08-18 2005-08-18 Beschichtungsmassen enthaltend mit Silanen modifizierte Nanopartikel
DE102006021705A DE102006021705B3 (de) 2006-05-10 2006-05-10 Verwendung von Mischoxid-Nanopartikeln in Beschichtungsmassen
PCT/EP2006/008066 WO2007020063A2 (fr) 2005-08-18 2006-08-16 Matieres d'enduction contenant des nanoparticules d'oxyde mixte

Publications (2)

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EP1922368A2 EP1922368A2 (fr) 2008-05-21
EP1922368B1 true EP1922368B1 (fr) 2016-12-21

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US (1) US20090173253A1 (fr)
EP (1) EP1922368B1 (fr)
JP (1) JP2009504857A (fr)
ES (1) ES2619252T3 (fr)
PL (1) PL1922368T3 (fr)
WO (1) WO2007020063A2 (fr)

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Publication number Priority date Publication date Assignee Title
ES2677894T3 (es) * 2005-07-16 2018-08-07 Archroma Ip Gmbh Procedimiento para la producción de nanopartículas de óxido de aluminio y óxidos de elementos del grupo principal I y II del sistema periódico
DE102005033393B4 (de) * 2005-07-16 2014-04-03 Clariant International Limited Verfahren zur Herstellung von nanokristallinem α-Al2O3
DE102005039435A1 (de) * 2005-08-18 2007-03-01 Clariant International Limited Verfahren zur Herstellung von mit Silanen oberflächenmodifiziertem Nanokorund
WO2007020064A1 (fr) * 2005-08-18 2007-02-22 Clariant International Ltd Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee
DE102006032582A1 (de) * 2006-07-13 2008-01-24 Clariant International Limited Verfahren zur Herstellung von Nanopartikeln aus Aluminiumspinellen und deren Anwendung
WO2008022760A1 (fr) * 2006-08-24 2008-02-28 Clariant Finance (Bvi) Limited Encres d'impression contenant des nanoparticules d'oxyde mixte
DE102006045816A1 (de) * 2006-09-28 2008-04-03 Clariant International Limited Polykristalline Korundfasern und Verfahren zu deren Herstellung
DE102006054013A1 (de) * 2006-11-16 2008-05-21 Clariant International Ltd. Beschichtungsmassen enthaltend reaktive Esterwachse und Mischoxid-Nanopartikel
US7758961B2 (en) * 2007-03-22 2010-07-20 Milliken & Company Functionalized nanoparticles and their use in particle/bulk material systems
NO328788B1 (no) * 2008-03-14 2010-05-18 Jotun As Bindemiddel til lufttørkende maling
DE102011115025A1 (de) * 2011-10-07 2013-04-11 Ask Chemicals Gmbh Beschichtungsmassen für anorganische Gießformen und Kerne enthaltend Salze und deren Verwendung
US9308616B2 (en) 2013-01-21 2016-04-12 Innovative Finishes LLC Refurbished component, electronic device including the same, and method of refurbishing a component of an electronic device
KR101750398B1 (ko) * 2014-01-02 2017-06-23 삼성전자주식회사 광산란층 제조 방법
US10480281B2 (en) 2016-11-15 2019-11-19 Saudi Arabian Oil Company Nanoparticle-based shear-thickening materials
WO2022051628A1 (fr) 2020-09-03 2022-03-10 Saudi Arabian Oil Company Injection de multiples fluides à marqueur de traçage dans un puits de forage
US11660595B2 (en) 2021-01-04 2023-05-30 Saudi Arabian Oil Company Microfluidic chip with multiple porosity regions for reservoir modeling
US11534759B2 (en) 2021-01-22 2022-12-27 Saudi Arabian Oil Company Microfluidic chip with mixed porosities for reservoir modeling

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1068836B (de) * 1959-11-12 Badische Bau- und Kunststoff G.m. b.H., Mannheim-Feudenheim Verwendung im regulären Kristallsystem kristallisierter, spinellartiger Verbindungen als Pigmente oder Füller
JPH06104816B2 (ja) * 1990-02-09 1994-12-21 日本研磨材工業株式会社 焼結アルミナ砥粒及びその製造方法
BR9408041A (pt) * 1993-11-12 1996-12-24 Minnesota Mining & Mfg Processo para preparação de grão abrasivo à base de alumina alfa cerâmico cristalino grão abrasivo e artigo abrasivo
US20030077221A1 (en) * 2001-10-01 2003-04-24 Shivkumar Chiruvolu Aluminum oxide powders
DE19846660A1 (de) * 1998-10-09 2000-04-13 Inst Oberflaechenmodifizierung Hochtemperaturbeständige polymerisierbare Metalloxidpartikel
DE19922492A1 (de) * 1999-05-14 2000-11-16 Fraunhofer Ges Forschung Verfahren zur Herstellugn von Aluminiumoxiden und daraus hergestellten Produkten
WO2001064796A1 (fr) * 2000-02-29 2001-09-07 Aluminium Féron Gmbh & Co. Peinture, matiere stratifiee produite avec ladite peinture et procede de production de ladite matiere stratifiee
US6896958B1 (en) * 2000-11-29 2005-05-24 Nanophase Technologies Corporation Substantially transparent, abrasion-resistant films containing surface-treated nanocrystalline particles
DE10149130A1 (de) * 2001-10-05 2003-04-10 Degussa Flammenhydrolytisch hergestelltes, mit zweiwertigen Metalloxiden dotiertes Aluminiumoxid und wässerige Dispersion hiervon
FR2831156B1 (fr) * 2001-10-18 2004-02-20 Pechiney Aluminium Alumine calcinee broyee destinee a entrer dans la composition d'un precurseur pour materiau refractaire, et procede d'obtention de ladite alumine
US20030148042A1 (en) * 2001-12-28 2003-08-07 Zhikai Wang Ultrasonic method for the production of inorganic/organic hybrid nanocomposite
DE10304849A1 (de) * 2003-02-06 2004-08-19 Institut für Neue Materialien gemeinnützige Gesellschaft mit beschränkter Haftung Chemomechanische Herstellung von Funktionskolloiden
JP2005171199A (ja) * 2003-12-15 2005-06-30 Toyota Motor Corp 微塩基性アルミナ粉体、その製造方法及び樹脂組成物
DE102005039436B4 (de) * 2005-08-18 2009-05-07 Clariant International Limited Beschichtungsmassen enthaltend mit Silanen modifizierte Nanopartikel
DE102005033393B4 (de) * 2005-07-16 2014-04-03 Clariant International Limited Verfahren zur Herstellung von nanokristallinem α-Al2O3
ES2677894T3 (es) * 2005-07-16 2018-08-07 Archroma Ip Gmbh Procedimiento para la producción de nanopartículas de óxido de aluminio y óxidos de elementos del grupo principal I y II del sistema periódico
DE102005039435A1 (de) * 2005-08-18 2007-03-01 Clariant International Limited Verfahren zur Herstellung von mit Silanen oberflächenmodifiziertem Nanokorund
WO2007020064A1 (fr) * 2005-08-18 2007-02-22 Clariant International Ltd Nanoparticules a surface modifiee, constituees par un oxyde d'aluminium et des oxydes d'elements du i. ou ii. groupe principal de la classification periodique des elements et realisation associee
DE102006045816A1 (de) * 2006-09-28 2008-04-03 Clariant International Limited Polykristalline Korundfasern und Verfahren zu deren Herstellung

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WO2007020063A3 (fr) 2007-07-19
US20090173253A1 (en) 2009-07-09
WO2007020063A2 (fr) 2007-02-22
JP2009504857A (ja) 2009-02-05
PL1922368T3 (pl) 2017-06-30
EP1922368A2 (fr) 2008-05-21

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